JP5246754B2 - Luminescent phosphor and method for producing the same - Google Patents

Description

  The present invention relates to a phosphorescent phosphor containing a rare earth element as an activator and a method for producing the same.

  A phosphorescent phosphor that is one type of phosphor emits light in the dark by absorbing light such as sunlight and storing its energy. In the past, non-oxide materials containing copper or the like in zinc sulfide (for example, ZnS: Cu) were mainstream, but in recent years, rare earth elements have been added to ceramic materials mainly composed of aluminum oxide. Oxide materials having a long light emission time have been developed and are mainly used.

As a phosphorescent phosphor containing a rare earth element in a ceramic material, a material in which europium (Eu) and dysprosium (Dy) are contained in strontium aluminate (SrAl ₂ O ₄ : Eu, Dy) is well known. Yes. SrAl ₂ O ₄ : Eu, Dy is currently most popular as a phosphorescent phosphor because it has a better afterglow luminance and duration than ZnS: Cu.

In recent years, a photocatalyst capable of causing a chemical reaction difficult at ordinary temperatures in a normal catalytic process has attracted attention. A photocatalyst is a general term for substances that exhibit catalytic action when irradiated with light, as the name suggests. Among such photocatalysts, titanium oxide (TiO ₂ ) is known as a typical photocatalyst. Titanium oxide is a substance that is expected to be applied not only to chemical reactions but also to a wide range of fields such as destruction of cancer cells by photoreaction. However, as a matter of course, the photocatalyst does not exhibit catalytic activity in a place where light does not reach, such as in the body or a dark room. Therefore, for example, for use in medical applications such as destroying cancer cells in the body, it is necessary to improve the catalytic activity even in places where the light does not reach such as in the body.

A substance expected to be suitably used for improving such a photocatalyst is the above-described phosphorescent phosphor. That is, it is considered that the photocatalyst can be activated even in a dark place such as the inside of the body by combining the phosphorescent phosphor and the photocatalyst. Moreover, since the phosphorescent phosphor is an oxide as described above, it is considered that the phosphorescent phosphor is also compatible with titanium oxide, which is also an oxide.
Mitsuo Yamake, Nobuhiro Kodama, Ceramics, 42, (2007), No. 11, 856-861 N. Kodama et al., Appl. Phys. Lett., Vol.75, No.12,1715-1717, 20 September 1999

However, the wavelength at which titanium-based oxides including titanium oxide known as a photocatalyst are activated is about 410 nm or less, whereas SrAl ₂ O _4, which is most popular as a phosphorescent phosphor: The emission wavelengths of Eu and Dy are 520 nm. Further, among the phosphorescent phosphors which are currently commercially available, the emission wavelength is the shortest CaAl ₂ O _4: Eu, the emission wavelength even Nd is 440 nm. That is, the photocatalyst cannot be activated with the phosphorescent phosphors that are currently widely used. Therefore, there is a need for a short wavelength phosphorescent phosphor having higher energy than the phosphorescent phosphor described above.

Non-Patent Documents 1 and 2 describe phosphorescent phosphors containing cerium (Ce) in the base crystal as phosphorescent phosphors having emission wavelengths shorter than those of CaAl ₂ O ₄ : Eu, Nd. . Comprising a Ce to host crystals _{Ca 2 Al 2 SiO 7 Ca 2} Al 2 SiO 7: emission wavelength of Ce is 417 nm, comprising a Ce to host crystal _{CaYAl 3 O 7 CaYAl 3 O 7} : Ce Has an emission wavelength of 425 nm (see, for example, Non-Patent Document 2). Thus, even in the phosphorescent phosphor containing cerium as described in Non-Patent Documents 1 and 2, the emission wavelength is about 410 to 420 nm, and the titanium-based oxide is activated. It cannot be said that the wavelength is sufficient for the purpose. In addition, the development of phosphorescent phosphors with higher emission intensity is also desired.

  This invention is made | formed in view of the said subject, The main objective is improving luminous intensity and providing the luminous phosphor with a light emission wavelength smaller than 410 nm.

  In order to achieve the above object, the present inventors have paid attention to the inclusion of a plurality of rare earth elements in the base crystal. And as a result of earnestly examining the combination of rare earth elements to be included, the present inventors have made thulium one of the rare earth elements to be included, and compared with the phosphorescent phosphor when no thulium is contained. Thus, the present inventors have found that the emission intensity can be improved and the emission wavelength can be changed, and the present invention has been completed.

  The present invention has been completed based on such new knowledge, and includes the following inventions.

In order to solve the above problems, the phosphorescent phosphor according to the present invention is
A phosphorescent phosphor comprising a host crystal containing a plurality of types of rare earth elements, wherein one of the rare earth elements is thulium.

  In the phosphorescent phosphor containing a plurality of kinds of rare earth elements, by making one of the rare earth elements thulium (Tm), the emission intensity of the obtained phosphorescent phosphor can be improved and its emission wavelength Can be made shorter than 410 nm.

  Thereby, for example, a photocatalyst of titanium-based oxide such as titanium oxide can be sufficiently activated.

In the phosphorescent phosphor according to the present invention, preferably, the base crystal is Ca ₂ Al ₂ SiO ₇ and the rare earth elements are cerium and thulium.

By using Ca ₂ Al ₂ SiO ₇ as the base crystal and cerium and thulium as the rare earth elements to be contained, there is an effect that the emission intensity can be improved up to about four times as compared with the case where thulium is not included. In addition, the emission wavelength can be shortened to 404 nm.

  In the phosphorescent phosphor according to the present invention, the thulium ion content is preferably in the range of 0.01 to 0.50 mol%.

  By setting the thulium content within the above range, the luminous intensity of the phosphorescent phosphor can be further improved.

In order to solve the above problems, a method for producing a phosphorescent phosphor according to the present invention is as follows.
Including a firing step of firing a phosphorescent phosphor material containing an oxide of a plurality of types of rare earth elements and a material forming a host crystal in a reducing gas atmosphere, and one of the oxides is It is characterized by being thulium oxide.

  According to said structure, the luminous phosphor which concerns on this invention can be manufactured. Therefore, the same effect as the phosphorescent phosphor according to the present invention is exhibited.

  In the method for producing a phosphorescent phosphor according to the present invention, the phosphorescent phosphor material further comprises an alcohol obtained by pulverizing a mixture containing a plurality of types of rare earth element oxides and a material forming a host crystal. It is preferable to knead together.

  By pulverizing and kneading a mixture containing a plurality of types of rare earth element oxides and a material that forms a parent crystal together with alcohol, the oxide and the material that forms the parent crystal are more easily mixed. There is an effect that can be.

  In the method for producing a phosphorescent phosphor according to the present invention, it is preferable that the phosphorescent phosphor material further contains calcium carbonate, aluminum oxide, boric acid, silicon dioxide, cerium oxide, and thulium oxide.

According to the above _{configuration, Ca 2 Al 2 SiO 7:} Ce, an effect which can be suitably prepared Tm.

  In the method for producing a phosphorescent phosphor according to the present invention, the alcohol is preferably ethanol.

  Since ethanol is harmless to the human body, the use of ethanol as the alcohol used for kneading has the effect of easily producing a phosphorescent phosphor. Moreover, since ethanol is easy to dry, the process of drying the kneaded mixture can be omitted. That is, there is an effect that the time required for manufacturing the phosphorescent phosphor can be shortened.

  In the method for producing a phosphorescent phosphor according to the present invention, it is preferable that the firing step is performed a plurality of times.

  According to said structure, there exists an effect that the uniformity of the composition of the luminous fluorescent substance obtained can be improved.

  As described above, the present invention is characterized in that one of a plurality of types of rare earth elements contained in the host crystal is thulium.

  As a result, the luminous intensity of the obtained phosphorescent phosphor can be improved, and the emission wavelength can be made shorter than 410 nm.

  One embodiment of the phosphorescent phosphor according to the present invention will be described below.

  The phosphorescent phosphor according to the present embodiment is a phosphorescent phosphor containing a plurality of types of rare earth elements in a host crystal, and one of the rare earth elements to be contained is thulium. .

Here, in this specification and the like, a phosphorescent phosphor containing a rare earth element in a host crystal is also expressed as “macrocrystal molecular formula: element symbol of rare earth element”. In addition, when there are a plurality of rare earth elements to be included, the element symbols of the rare earth elements are distinguished by separating them with commas (,). For example, a phosphorescent phosphor whose base crystal is Ca ₂ Al ₂ SiO ₇ and whose rare earth element is Ce is represented as “Ca ₂ Al ₂ SiO ₇ : Ce”, and the base crystal is Ca ₂ Al ₂ SiO ₇ . A phosphorescent phosphor having rare earth elements Ce and Tm is denoted as “Ca ₂ Al ₂ SiO ₇ : Ce, Tm”.

(Matrix and rare earth elements)
In the present specification and the like, “matrix crystal” refers to a crystal having a phosphorescent function by containing at least one kind of rare earth element as an activator.

The base crystal that can be suitably used in the present invention is not particularly limited in its structure and type as long as it contains a rare earth element and has a phosphorescent function. Examples of the base crystal include calcium aluminosilicates such as Ca ₂ Al ₂ SiO ₇ , Ca ₂ Al ₃ Si ₂ O ₇ , and Ca _1.96 Al ₂ Si _1.02 O ₇ , CaYAl ₃ O ₇ , and CaNaAlSi ₂ O _7. , (Ca, Na) ₂ (Al, Mg) (Si, Al) ₂ O ₇ , Ca ₂ MgSi ₂ O ₇ , Ca ₂ BeSi ₂ O ₇ , Ca ₂ (Mg, Fe) Si ₂ O ₇ , Ca ₂ B ₂ SiO ₇ or the like can be used. Among these, calcium aluminosilicate is preferable, and Ca ₂ Al ₂ SiO ₇ is more preferable. Here, “calcium aluminosilicate” in this specification and the like is represented by the general formula xCaO.yAl ₂ O 3 .zSiO ₂ . That is, Ca ₂ Al ₂ SiO ₇ is a case where x = 1, y = 1, and z = 1 in the above general formula.

Of the rare earth elements contained in the host crystal as an activator, the rare earth elements other than thulium are not particularly limited and can be appropriately changed according to the type of the host crystal. As rare earth elements other than thulium, for example, cerium, praseodymium, samarium, europium, terbium, ytterbium, and the like can be used. For example, when the base crystal is Ca ₂ Al ₂ SiO ₇ , the rare earth element to be contained is preferably thulium and cerium. Furthermore, the kind of rare earth elements contained in the host crystal is not particularly limited as long as it is a plurality of kinds, that is, two or more kinds, and may be three kinds or more.

(Range of thulium content)
The thulium content in the phosphorescent phosphor is preferably in the range of 0.01 to 0.50 mol%, and more preferably in the range of 0.01 to 0.1 mol%.

  By setting the thulium content within the above range, the light emission intensity of the phosphorescent phosphor can be further improved.

When the base crystal is Ca ₂ Al ₂ SiO ₇ and the rare earth elements to be contained are cerium (Ce) and thulium (Tm) (that is, Ca ₂ Al ₂ SiO ₇ : Ce, Tm), When the content is 0.06 mol%, the luminous intensity of the phosphorescent phosphor becomes the maximum value (about 105 cps). This is about 4.2 times the emission intensity when not containing thulium, that is, Ca ₂ Al ₂ SiO ₇ : Ce.

  Further, the content of rare earth elements other than thulium is not particularly limited, and may be set as appropriate according to the host crystal to be used. In addition, the “content of rare earth element (thulium)” in this specification and the like means the content of rare earth element with respect to the entire phosphorescent phosphor.

(Method for producing phosphorescent phosphor)
The method for producing a phosphorescent phosphor according to the present invention includes at least a firing step of firing a phosphorescent phosphor material containing a plurality of types of rare earth element oxides and a material forming a host crystal in a reducing atmosphere. Contains. Details of the firing step will be described in detail below.

  Conditions in the firing step can be set as appropriate according to the phosphorescent phosphor to be produced. For example, the firing temperature is preferably in the range of 800 to 1600 ° C, and more preferably in the range of 1100 to 1500 ° C. The firing time is preferably in the range of 1 to 24 hours, and more preferably in the range of 3 to 5 hours.

  By setting the firing temperature and firing time within the above ranges, the phosphorescent phosphor according to the present invention can be suitably produced.

  The firing step is preferably performed a plurality of times. At this time, the condition may be changed as long as it is within the range of the above condition. Of course, you may perform a baking process in multiple times, without changing conditions. By performing the firing step a plurality of times, the uniformity of the composition of the obtained phosphorescent phosphor can be improved.

  The apparatus for firing is not particularly limited as long as the apparatus can realize the firing conditions described above. An example of such an apparatus is an electric furnace.

  The “reducing atmosphere” in this specification and the like is not particularly limited as long as it is an atmosphere that causes a reduction reaction. Specific examples of the reducing atmosphere include an atmosphere of 95% argon and 5% hydrogen. Moreover, argon 100% or nitrogen 100% can also be mentioned.

The rare earth element oxide which is one of the phosphorescent phosphor materials of the phosphorescent phosphor according to the present invention is not particularly limited as long as it is an oxide containing the rare earth element described above. For example, thulium oxide can include thulium oxide (Tm ₂ O ₂ ), and cerium oxide can include cerium oxide (CeO ₂ ).

In addition, a material for forming a host crystal, which is one of the light-emitting phosphor materials, can be appropriately set according to the type of the host crystal to be formed. For example, when Ca ₂ Al ₂ SiO ₇ is used as the base crystal, it is preferable to use calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), and silicon dioxide (SiO ₂ ).

The phosphorescent phosphor material preferably contains boric acid (H ₃ BO ₃ ) as a sintering aid in addition to these materials.

  The phosphorescent phosphor material in the phosphorescent phosphor according to the present invention is obtained by pulverizing and kneading a mixture containing an oxide of a plurality of types of rare earth elements and a material forming a host crystal together with alcohol. It is preferable. A mixture containing a plurality of types of rare earth oxides that can make it easier to mix the oxide and the material forming the parent crystal and the material forming the parent crystal is pulverized and kneaded with alcohol. As a result, the oxide and the material forming the host crystal can be more easily mixed.

  For kneading the phosphorescent phosphor material, for example, a mortar, a mixer, a ball mill, or the like can be used. The alcohol that can be used for kneading is not particularly limited, and for example, ethanol, methanol, propanol, butanol, bentanol, ethylene glycol, isopropyl alcohol, glycerin, cetanol, ester, or the like may be used. it can. Among these, ethanol is more preferable. Since ethanol is harmless to the human body, a phosphorescent phosphor can be easily produced by using ethanol as the alcohol used for kneading. Moreover, since ethanol is easy to dry, it is not necessary to dry the kneaded mixture. Therefore, the time required for manufacturing the phosphorescent phosphor can be shortened.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims. That is, embodiments obtained by combining technical means appropriately modified within the scope of the claims are also included in the technical scope of the present invention.

  Hereinafter, an Example is shown and it demonstrates in more detail about the form of this invention. Of course, the present invention is not limited to the following examples, and various modes are possible for details.

[Example 1]
A method for producing Ca ₂ Al ₂ SiO ₇ : Ce, Tm, which contains cerium and thulium as activators in Ca ₂ Al ₂ SiO ₇ will be described as Example 1.

First, calcium carbonate (CaCO ₃ ) (1.9617 g; 0.0196 mol), aluminum oxide (Al ₂ O ₃ ) (1.0198 g; 0.01 mol), silicon dioxide (SiO ₂ ) (0.6127 g; 0.0102 mol) ), Cerium oxide (CeO ₂ ) (0.0172 g; 1 × 10 −4 mol), thulium oxide (Tm ₂ O ₃ ) (0.0018 g; 4.7 × 10 −6 mol), and boric acid (H ₃ BO ₃ ) (0.1237 g; 0.002 mol) was mixed in a mortar and molded. And it baked at 1400 degreeC for 3 hours using the electric furnace in the reducing atmosphere. In this example, the reducing atmosphere was an atmosphere of 95% argon and 5% hydrogen.

[Comparative Examples 1 to 13]
One of the rare earth elements to be contained is thulium to yttrium (Comparative Example 1), lanthanum (Comparative Example 2), praseosium (Comparative Example 3), neodymium (Comparative Example 4), samarium (Comparative Example 5), europium (Comparative Example 6). ), Gadolinium (Comparative Example 7), Terbium (Comparative Example 8), Dysprosium (Comparative Example 9), Holmium (Comparative Example 10), Erbium (Comparative Example 11), Ytterbium (Comparative Example 12), Lutetium (Comparative Example 13) A phosphorescent phosphor was produced using the same method as in Example 1 except that the phosphor was changed to.

(Difference in emission intensity due to differences in rare earth elements contained with cerium)
FIG. 1 shows the result of measuring the emission intensity after 100 seconds after irradiating the phosphorescent phosphors produced in Example 1 and Comparative Examples 1 to 13 with light.

FIG. 1 is a diagram showing the emission intensity in each phosphorescent phosphor when Ca ₂ Al ₂ SiO ₇ which is a base crystal contains various rare earth elements together with cerium. Incidentally, as a target to be compared with each phosphorescent _phosphor, when was contained only cerium against Ca ₂ Al ₂ SiO _{7 (i.e., Ca 2 Al 2 SiO 7:} Ce) was also measured emission intensity of. Ca ₂ Al ₂ SiO ₇ : Ce can be produced by a conventionally known production method.

As shown in FIG. 1, as compared with Ca ₂ Al ₂ SiO ₇ : Ce, only when cerium and thulium are contained in Ca ₂ Al ₂ SiO ₇ (that is, in the case of Example 1). Only), an improvement in emission intensity could be observed. More specifically, the emission intensity of Ca ₂ Al ₂ SiO ₇ : Ce containing only cerium was 14 cps, and only when further containing thulium, the emission intensity exceeding 21 cps was shown.

On the other hand, when a rare earth element other than thulium is contained together with cerium (that is, in the case of Comparative Examples 1 to 13), the emission intensity is compared with Ca ₂ Al ₂ SiO ₇ : Ce containing only cerium. Was weak.

Thereby, it was shown that the luminous intensity of the phosphorescent phosphor can be further increased by further containing thulium with respect to Ca ₂ Al ₂ SiO ₇ : Ce.

[Example 2]
(Change in emission intensity due to change in thulium content)
Ca ₂ Al ₂ SiO ₇ : Ce, Tm was produced in the same manner as in Example 1 except that the amount of thulium oxide to be used was variously changed. Then, in the same manner as in Example 1, the light emission intensity after 100 seconds was measured after the phosphorescent phosphor was irradiated with light. The mole of thulium oxide used is equal to the thulium content in the phosphorescent phosphor.

  The relationship between the thulium content and the emission intensity of the phosphorescent phosphor is shown in FIGS. 2 (a) and 2 (b). 2 (a) and 2 (b) are diagrams showing the relationship between the thulium content and the luminous intensity of the phosphorescent phosphor, (a) showing the luminous intensity for each thulium content, (B) has shown the change of the emitted light intensity by changing content of thulium.

  As shown in FIGS. 2 (a) and (b), the emission intensity of the phosphorescent phosphor was changed by variously changing the amount of thulium to be contained. In particular, as shown in FIGS. 2 (a) and 2 (b), the light emission intensity of the phosphorescent phosphor could be improved by containing a small amount of thulium as compared with the case where no thulium was contained.

From the viewpoint of improving the emission intensity, it has been shown that thulium can further improve the emission intensity of the phosphorescent phosphor within the range of 0.01 to 0.50 mol%. When the thulium content was 0.06 mol%, the luminous intensity of the phosphorescent phosphor reached the maximum value (about 105 cps). In the case where thulium was not contained, that is, the emission intensity was about 4.2 times that of Ca ₂ Al ₂ SiO ₇ : Ce.

Example 3
(Change in luminous intensity of phosphorescent phosphor over time)
FIG. 3 shows the change in emission intensity of each phosphorescent phosphor over time with Ca ₂ Al ₂ SiO ₇ : Ce and Ca ₂ Al ₂ SiO ₇ : Ce, Tm. In addition, the horizontal axis (time axis) in FIG. 3 represents the time elapsed since the irradiation of light to each phosphorescent phosphor was completed. The vertical axis represents relative intensity, and the unit is arbitrary. Ca ₂ Al ₂ SiO ₇ : Ce, Tm was manufactured using the same method as in Example 1.

As shown in FIG. 3, the emission intensity of Ca ₂ Al ₂ SiO ₇ : Ce, Tm is higher than that of Ca ₂ Al ₂ SiO ₇ : Ce at any time from 0 to 100 seconds after the end of light irradiation. Was getting stronger. _That, Ca ₂ Al _{2 SiO} 7: compared with _{Ce, Ca 2 Al 2 SiO 7} : Ce, found the following Tm, while improving the luminous intensity of the phosphorescent phosphor to allow more prolonged emission It was shown that it can.

Example 4
(Ca ₂ Al ₂ SiO ₇ : Ce, emission wavelength of Tm)
The emission wavelength of Ca ₂ Al ₂ SiO ₇ : Ce, Tm was 404 nm. The emission wavelength of Ca ₂ Al ₂ SiO ₇ : Ce measured using the same apparatus was 406 nm. This showed that the emission wavelength was shortened by the addition of Tm.

Example 5
Ca _1.96 Al ₂ Si _1.02 O ₇ : Ce, Tm was produced in the same manner except that the production method and composition of Ca ₂ Al ₂ SiO ₇ : Ce, Tm were changed. After irradiating light in Ca _1.96 Al ₂ Si _1.02 O ₇ : Ce, Tm, the emission intensity after 100 seconds is 27 cps, which is higher than the emission intensity of Ca ₂ Al ₂ SiO ₇ : Ce, Tm. It was big.

  The phosphorescent phosphor according to the present invention can be applied to a wide range of uses such as a light source for activating a photocatalyst such as titanium oxide.

Is a graph showing an emission intensity at each phosphorescent phosphor in the case of Ca ₂ Al ₂ SiO ₇ further contain a variety of rare earth elements with a cerium respect. It is a figure which shows the relationship between thulium content and the luminous intensity of phosphorescent phosphor, (a) shows the luminous intensity with respect to each content of thulium, (b) changes thulium content The change of the luminescence intensity by making it show is shown. Ca ₂ and Al ₂ formed by incorporating only cerium SiO ₇ phosphorescent _phosphors shows changes in emission intensity over time of the Ca ₂ Al 2 SiO ₇ in phosphorescent phosphors which contains cerium and thulium FIG.

Claims (5)

A phosphorescent phosphors host crystal comprises a plurality of kinds of rare earth elements, one of the rare earth element, Ri thulium der,
A phosphorescent phosphor characterized in that the base crystal is Ca ₂ Al ₂ SiO ₇ and the rare earth elements are cerium and thulium . The phosphorescent phosphor according to claim 1 , wherein the thulium content is in the range of 0.01 to 0.50 mol%. Including a firing step of firing a phosphorescent phosphor material containing a plurality of types of rare earth element oxides and a material forming a host crystal in a reducing gas atmosphere,
The phosphorescent phosphor material is a mixture containing a plurality of types of rare earth element oxides and a material forming a host crystal, pulverized, and kneaded with alcohol.
One of the oxides, Ri thulium oxide der, and
The phosphorescent phosphor material comprises calcium carbonate, aluminum oxide, boric acid, silicon dioxide, cerium oxide, and thulium oxide . The method for producing a phosphorescent phosphor according to claim 3 , wherein the alcohol is ethanol. The method for producing a luminous phosphor according to claim 3 or 4 , wherein the firing step is performed a plurality of times.

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